Acrylated epoxidized soybean oil urethane derivatives

ABSTRACT

The urethane derivatives of acrylated epoxidized soybean oil, which is the reaction product of epoxidized soybean oil with acrylic acid or methacrylic acid, are produced by the reaction of acrylated epoxidized soybean oil with an organic isocyanate. The derivatives are useful alone, or in conjunction with a photosensitizer, and/or a pigment as inks and coatings. The ink and coating compositions can be cured by radiation.

This application is a division of Ser. No. 343,694, filed Mar. 22, 1973,which was a division of Ser. No. 103,912, filed Jan. 4, 1971, nowabandoned.

BACKGROUND OF THE INVENTION

The epoxide derivatives of esters of soybean oil are known; also knownare the acrylyl derivatives thereof. Such derivatives have also beenused in the production of epoxide resins and in coating compositions;however, the coatings do not meet all of the requirements necessary intoday's advanced technology.

SUMMARY OF THE INVENTION

It has now been found that certain urethane derivatives of acrylatedepoxidized soybean oil compounds and certain amine derivatives ofacrylated epoxidized soybean oil compounds can be produced and that suchderivatives are in themselves useful as coatings, adhesives, moldingcompositions, and the like, or they can be used in combination withother materials to produce compositions that are similarly useful.

DESCRIPTION OF THE INVENTION

The urethane derivatives of the acrylated epoxidized soybean oilcompounds are produced by the reaction of an organic mono- orpoly-isocyanate with the acrylated epoxidized soybean oil compound.Among the isocyanates that can be used in producing these derivativesare those represented by the general formula:

    R(NCO).sub.x

wherein R can be an alkyl group of from 1 to about 15 carbon atoms, asubstituted or unsubstituted mono- or polycycloalkyl group of from 5 toabout 12 carbon atoms, or a substituted or unsubstituted aryl grouphaving from 6 to about 12 carbon atoms. Illustrative thereof one canmention methyl isocyanate, ethyl isocyanate, butyl isocyanate,2-ethylhexyl isocyanate, chloroethyl isocyanate, cyclohexyl isocyanate,phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate,naphthyl isocyanate, o-ethylphenyl isocyanate, 2,4-tolylenediisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethanediisocyanate, polymethylene polyphenylisocyanate, dianisidinediisocyanate, 1,6-hexane diisocyanate, m-xylylene diisocyanate,dicyclohexyl-4,4'-methane diisocyanate, cyclohexane-1,4-diisocyanate,1,5-naphthalene diisocyanate,1-isocyanato-3-isocyanatomethyl-3,3,5-trimethylcyclohexane,diphenylene-4,4-diisocyanate, bicyclo[2.2.1]hept-2-en-5-isocyanate, andthe like. Any of the known organic isocyanates can be used, includingthe tri- and tetra-isocyanate compounds; all of these are well known tothose skilled in the art.

As previously indicated, the acrylated epoxidized soybean oil compoundsare known. These compounds, and the methods for their production, havebeen disclosed in U.S. Pat. Nos. 3,125,592 and 3,450,613; the teachingstherein are incorporated herein by reference. As is readily apparent,one can produce such compounds by the reaction of the epoxidized soybeanoil with acrylic acid or methacrylic acid; both are included within thescope of this invention but for convenience the discussion will be basedon the use of acrylic acid.

The reaction of the epoxidized soybean oil with acrylic acid proceedswith the opening of the epoxide ring in the molecule and the addition ofacrylic acid; this can be represented by the equation: ##STR1## Themethacrylyl group may be present instead of the acrylyl group. Thus, theacrylated epoxidized soybean oil compound contains an average of atleast two such acrylyl groups per molecule and, in addition, it may alsocontain some unreacted oxirane, preferably less than two weight percentunreacted oxirane.

The reaction of the acrylated epoxidized soybean oil compound with theisocyanato group is via the hydroxyl group to form a urethane link.Thus, the urethane derivatives of the acrylated epoxidized soybean oilcontain the group: ##STR2## where X is hydrogen or methyl. The number ofsuch groups present can be controlled by the amount of isocyanatecompound added to the reaction. All of the hydroxyl groups in theacrylated epoxidized soybean oil can be reacted with an isocyanatogroup, or less than all can be so reacted. Thus, from about 2 to about100 percent of the available hydroxyl groups can be converted tourethane groups; preferably from about 50 to about 90 percent thereofare reacted with the isocyanato group and converted to the urethanegroup. The polyisocyanates may react in intramolecular fashion with twohydroxyl groups on the same acrylated epoxidized soybean oil molecule orthey may serve to bridge or crosslink two of such molecules. It wasobserved that increased mono-urethane content in general providedenhanced toughness, and mar and water resistance, and decreasedviscosity; while increased intermolecular poly-urethane content in themolecule in general provided increased viscosity, increased crosslinkdensity, increased toughness and faster cure speed.

The reaction between the acrylated epoxidized soybean oil and theisocyanate can typically be carried out by the slow addition of theisocyanate to the acrylated epoxidized soybean oil compound. The orderof addition, however, is not critical. The temperature can be from about10° C. to about 100° C., preferably from about 20° C. to about 80° C.,and most preferably from about 40° C. to about 60° C. After the additionhas been completed, the reaction mixture is stirred to ensure completionof reaction. The time required will vary, of course, depending upon thesize of the batch, the reactants used, the temperature of the reactionand other variables known to affect chemical reactions in general. Asolvent can be present if desired. It is preferably an inert solventthat will not interfere with the reaction; these are well known andinclude ethers, hydrocarbons, ketones and esters such as diethyl ether,p-dioxane, dibutyl ether, tetrahydrofuran, diisopropyl ether, methylethyl ketone, methyl n-propyl ketone, methyl propionate, ethyl acetate,hexane, toluene, xylene, benzene, and the like. Of course, the presenceof water is known to be detrimental when an isocyanate group is involvedsince this group reacts readily and rapidly with water. Any one of theconventional catalysts known to promote the reaction of an isocyanatogroup with a reactive hydrogen atom of the hydroxyl group, can be used.The number of such catalysts is large, and illustrative thereof one canmention triethylamine, N,N,N',N'-tetramethylbutane-1,3-diamine,dibutyltin dilaurate, stannous octoate, stannous laurate, dioctyltindiacetate, lead octoate, bis[2-(N,N-dimethylamino)ethyl]ether,1,4-diazabicyclo[2.2.2]octane, and the like.

In the reaction of the acrylated epoxidized soybean oil compound with anamine compound, the amine compound is preferably a secondary amine ofthe formula R₂ 'NH, wherein each R' can be substituted or unsubstitutedalkyl having from 1 to about 15 carbon atoms, or an aryl group having upto 15 carbons, or the R_(2') unit together with the nitrogen atom of theNH group forms a ring structure having 5 or 6 ring atoms. Illustrativethereof one can mention dimethylamine, diethylamine, dibutylamine,dioctylamine, di-2-ethylhexylamine, diphenylamine,N-methyl-N-phenylamine, morpholine, piperidine, pyrrolidine, and thelike. In this reaction the amine compound adds across the double bond ofthe acrylyl unit of the acrylated epoxidized soybean oil compound toproduce a compound containing the group ##STR3##

The reaction between the secondary amine and the acrylated epoxidizedsoybean oil can be carried out by mixing the two compounds together andstirring at a temperature of from about 10° C. to about 100° C.; ambienttemperatures are preferred, thus eliminating any need for temperaturecontrol facilities. The amount of amine added can be an amountsufficient to react with from about 5 to 40 percent of the acrylylgroups present. If desired, an inert solvent, such as those heretoforementioned, can also be present.

The urethane derivatives of the acrylated epoxidized soybean oil and theamine derivatives of the acrylated epoxidized soybean oil can be usedper se as coating compositions, either alone or in admixture withconventional solvents, pigments, fillers and other additives. They canbe applied by conventional means and cured by exposure to heat, light,electron radiation, X-ray radiation, and other known means for curingand crosslinking a polymer, either alone or in the presence of acrosslinker.

The acrylated epoxidized soybean oil compounds, the urethane derivativesthereof and the amine derivatives thereof can also be used to producecoating compositions known as 100 percent reactive coating compositionsby mixing them with a reactive solvent. These reactive solvents are wellknown to those skilled in the art and include olefinic monomers such asstyrene, alpha-methylstyrene, p-methylstyrene, p-chlorostyrene, andacrylyl compounds such as the acrylate esters, the methacrylate esters,the acrylamides and the methacrylamides. These acrylyl compounds can berepresented by the formula: ##STR4## wherein Z is hydrogen or methyl; tis an integer having a value of 1 to 3; and R'" is alkoxy having from 1to about 18 carbon atoms (e.g., methoxy, ethoxy, propoxy, isopropoxy,2-methylhexoxy, 2-ethylhexoxy, decoxy, octadecoxy); hydroxyalkoxy havingup to about 15 carbon atoms (e.g., hydroxymethoxy, hydroxyethoxy,hydroxypropoxy, hydroxydecoxy); alkoxyalkoxy having up to a total ofabout 15 carbon atoms (e.g., methoxymethoxy, methoxyethoxy,ethoxybutoxy, methoxypropoxy, decoxypentoxy); cyano; cyanoalkoxy havingup to about 15 carbon atoms (e.g., cyanomethoxy, cyanobutoxy,cyanodecoxy); aryloxy (e.g., phenoxy, toloxy, xyloxy, phenoxyethoxy,naphthoxy, benzyloxy); or an --(OC_(n) H_(2n))_(z) NR""₂ group wherein nis an integer having a value of 1 to 10, z has a value of 0 or 1 and R""is alkyl having 1 to 10 carbon atoms when t is one or polyvalentalkylene or oxyalkylene having 2 to 8 carbon atoms in the alkylenemoiety thereof when t is other than one.

Illustrative of suitable acrylyl compounds, many more of which are wellknown in the art, one can mention methyl acrylate, ethyl acrylate,2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate,butyl acrylate, methoxybutyl acrylate, cyano acrylate, cyanoethylacrylate, phenyl acrylate, methyl methacrylate, propyl methacrylate,methoxyethyl methacrylate, ethoxymethyl methacrylate, phenylmethacrylate, ethyl methacrylate, lauryl methacrylate, N,N-dimethylacrylamide, N,N-diisopropyl acrylamide, N,N-didecyl acrylamide,N,N-dimethyl methacrylamide, N,N-diethyl methacrylamide,(N,N-dimethylamino)methyl acrylate, 2-(N,N-dimethylamino)ethyl acrylate,2-(N,N-dipentylamino)ethyl acrylate, (N,N-dimethylamino)methylmethacrylate, 2-(N,N-diethylamino)propyl acrylate, ethylene glycoldiacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate,1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethyleneglycol diacrylate, dipropylene glycol diacrylate, ethylene glycoldiacrylate, ethylene glycol dimethacrylate, propylene glycoldimethacrylate, diethylene glycol dimethacrylate, tripropylene glycoldiacrylate, trimethylolpropane triacrylate, pentaerythritroltriacrylate, and the like.

The concentration of reactive solvent in the 100 percent reactivecoating composition can be from zero to about 90 weight percent, withfrom 5 to 60 weight percent preferred, and from 10 to 50 weight percentmost preferred.

When the coating compositions are to be cured by light means they cancontain from about 0.1 to about 10 weight percent of an activator suchas any of the known photosensitizers or photoinitiators, preferably at aconcentration of from about one to about 5 weight percent. These can beadded singly or in mixtures and include, for example, benzophenone,p-methoxybenzophenone, acetophenone, m-chloroactophenone, propiophenone,xanthone, benzoin, benzil, benzaldehyde, naphthoquinone, anthraquinone,benzoin butyl ether, and the like.

If desired, an amine can also be present to further accelerate curing bylight radiation when the photoinitiator is an aryl ketone. Amines thatshow this synergistic rate-enhancing effect include triethanolamine,triisopropanolamine, methyldiethanolamine, tributylamine, triethylamineand the like.

The photoinitiators or photosensitizers are usually present at aconcentration of from about 0.1 to about 10 weight percent, preferablyfrom about 1 to about 5 weight percent, based on the weight of thecomposition. The amine accelerator, when present, is preferably presentat a concentration of from about 1 to about 10 weight percent, and canbe as high as 25 weight percent of the composition.

The coating compositions are produced by conventional methods by mixingthe selected components together. To facilitate preparation one canapply a small amount of heat. The coatings can be applied byconventional means, including spray, curtain, dip, pad, roll-coating andbrushing procedures. They may, if desired, be dried under ambient oroven conditions. The coatings can be applied to any acceptable substratesuch as wood, metal, glass, fabric, paper, fiber, plastic that is in anyform, e.g., sheet, coil, molded, film, panel, tube, etc.

The coating compositions containing the urethane derivatives ofacrylated epoxidized soybean oil or the amine derivatives of epoxidizedsoybean oil can be cured by exposure to heat or radiation, either beforeor after the coating has dried. The radiation can be ionizing radiation,either particulate or non-particulate, or non-ionizing radiation. As asuitable source of particulate radiation, one can use any source whichemits electrons or charged nuclei. Particulate radiation can begenerated from electron accelerators such as the Van de Graaffaccelerator, resonance transformers, linear accelerators, insulatingcore transformers, radioactive elements such as cobalt-60, strontium-90,etc. As a suitable source of non-particulate ionizing radiation, one canuse any source which emits light radiation in the range of from about10.sup.⁻³ Angstroms, to about 2000 Angstroms, preferably from about 5×10.sup.⁻³ Angstroms to about 1 Angstrom. Suitable sources are vacuumultraviolet lamps, such as xenon or krypton arcs, and radioactiveelements such as cesium-137, strontium-90 and cobalt-60. The nuclearreactors are also known to be a useful source of such radiation. As asuitable source of non-ionizing radiation, one can use any source whichemits radiation of from about 2000 Angstroms to about 4000 Angstroms,such as mercury arcs, carbon arcs, tungsten filament lamps, xenon arcs,krypton arcs, sunlamps, lasers, and the like. All of these devices andsources are well known in the art and those skilled in radiationtechnology are fully aware of the manner in which the radiation isgenerated and the precautions to be exercised in its use.

The use of low to high pressure mercury lamps to generate ultravioletlight is known. The largest such mercury lamp of commercial utility isgenerally about five feet long, having a diameter of about one to twoinches and an electrical input of about 20 kilowatts. Mercury lampsgenerate a typical ultraviolet light line structure.

The ionizing radiation dosage necessary to effect curing or crosslinkingof the coating composition will vary depending upon the composition ofthe particular coating that is undergoing radiation, the extent ofcrosslinking desired, the number of crosslinkable sites available andthe molecular weight of the starting polymer in the coating composition.The total dosage will generally be from about 10³ rads to 10⁸ rads,preferably from 5× 10⁵ rads to 10⁷ rads. A rad is 100 ergs of ionizingenergy absorbed per gram of material being irradiated.

Recently a source of light radiation emitting high intensitypredominantly continuum light radiation containing ultraviolet, visibleand infrared radiation was discovered that can be used to polymerizemonomers and to crosslink polymer compositions, namely the swirl-flowplasma arc radiation source. By means of proper light filters on thissource one can selectively screen out a portion of the light radiationemitted, permitting only that wavelength portion desired to reach thematerial being treated.

The term "high intensity predominantly continuum light radiation" meanscontinuum radiation with a source intensity of at least 350 watts persquare centimeter steradian (about 1000 kilowatts per square foot ofsource projected area) having only a minor part of the energy in peaksof bandwidths less than 100 Angstrom units, with less than about 30percent of the light radiated having wavelengths shorter than 4,000Angstrom units and at least about 70 percent of the light energyradiated having wavelengths longer than 4,000 Angstrom units.

This form of high intensity continuum light radiation is derived from anartificial source that generates high intensity predominantly continuumlight radiation with a source intensity of at least about 350 watts persquare centimeter steradian, as abbreviated by the term: watts cm.sup.⁻²sr.sup.⁻¹. Said high intensity predominantly continuum artificial lightradiation generally has about 70 percent of the light radiated at awavelength longer than 4,000 Angstroms and less than about 30 percent ofthe light radiated having a wavelength shorter than 4,000 Angstroms,usually, however, about 80 percent of the light radiated has awavelength longer than 4,000 Angstroms and less than about 20 percent ofthe light radiated has a wavelength shorter than 4,000 Angstroms, andthe source intensity can vary from about 350 watts (about 1000 kilowattsper square foot of source projected area) to about 5,000 watts (about15,000 kilowatts per square foot of source projected area) or more persquare centimeter steradian. A convenient source of high intensitypredominantly continuum light radiation is a swirl-flow plasma arc lightradiation apparatus. The equipment for generating high intensitypredominantly continuum light radiation by this means is known andavailable; many different forms thereof are described in the literature.A highly efficient apparatus for obtaining high intensity predominantlycontinuum light radiation is the swirl-flow plasma arc radiation sourcedescribed in U.S. Pat. No. 3,364,387. The apparatus or equipmentnecessary for generating the light radiation is not the subject of thisinvention and any source or apparatus capable of generating highintensity predominantly continuum light radiation can be used.

While any artificial source of generating high intensity predominantlycontinuum light radiation can be used, as previously indicated theswirl-flow plasma arc radiation apparatus is most convenient. Anyapparatus that operates according to the known principles of theswirl-flow plasma arc radiation source can be used to produce the highintensity predominantly continuum light radiation useful in the curingor crosslinking process or this invention. These apparatuses are oftenknown by other terms but those skilled in this art recognize that theyemit high intensity predominantly continuum light radiation. The sourceof radiation in a 50 kilowatt swirl-flow plasma arc radiation source isan arc only about four inches long enclosed in a quartz envelope about1.5 inches in diameter. This lamp can be readily removed and refurbishedand has an acceptable long lifetime. Further, a swirl-flow plasma arcradiation apparatus having a 250 kilowatt rating would be only about twoor three times as large as a 50-kilowatt source. Another advantage isthe absence of a need for expensive radiation shielding. Precautionsrequired for the artificial light sources include those needed toprotect one's eyes from the intense visible light and from theultraviolet light present to prevent inadvertent sunburn effect on thebody.

It is to be noted that in the spectra of high intensity predominantlycontinuum light radiation there is a continuum of radiation throughoutthe entire spectral range. This type of continuum radiation in theultraviolet range has not heretofore been obtainable from theconventional commercial mercury arcs of lamps generally available forgenerating ultraviolet light. The previously known means for generatingultraviolet light produced light that shows a line or peak spectrum inthe ultraviolet range, it is not a continuum spectrum in the ultravioletrange. In a line spectrum the major portion of useable ultraviolet lightis that portion at which the line or band in the spectrum forms a peak;in order for such energy to be useful the material or composition thatis to be treated with ultraviolet radiation must be capable of absorbingat that particular wavelength range at which the peak appears. In theevent the material or composition does not have the ability to absorb atthat particular wavelength range there is little or no absorption orreaction. Thus, in the event the material or composition to be treatedabsorbs at a particular wavelength range in one of the valleys of thespectral curve there will be little or no reaction since there is littleor no ultraviolet energy to adequately excite the system. With a highintensity predominantly continuum radiation, there is a high intensitycontinuum radiation of ultraviolet energy across the entire ultravioletwavelength range of the spectrum and there is generally sufficientultraviolet energy generated at all useful ultraviolet wavelengths toenable one to carry out reactions responsive to ultraviolet radiationwithout the problem of selecting compound that will absorb at the peakwavelength bands only. With the high intensity continuum radiation nowdiscovered one does not have the problem of being unable to reactmaterials or compositions that absorb in the valley areas only since forall intents and purposes such valleys do not exist in high intensitycontinuum radiation, the high intensity radiated light energy isessentially a continuum, it is not in peak bands.

High intensity predominantly continuum light radiation is to bedistinguished from ultraviolet radiation generated by commerciallyavailable low, medium and high pressure mercury arc ultraviolet lamps.These mercury arc lamps produce light emission which is primarily lineor peak rather than continuum light, wherein a major part of the lightappears in bands narrower than 100 Angstrom units, and much less than 70percent is above 4,000 Angstrom units.

As is known, high intensity predominantly continuum light radiation froma swirl-flow plasma arc radiation source is emitted from an arcgenerated between a pair of electrodes that are lined up axially andencased in a quartz cylinder. In an embodiment a pair of concentricquartz cylinders between which cooling water or gas flows is used. Arare gas, such as argon, krypton, neon or xenon, introduced into theinner cylinder tangentially through inlets located at one end of theinner cylinder creates a swirling flow or vortex which restricts the arcto a small diameter. An electrical potential applied across theelectrodes causes a high density current to flow through the gas togenerate a plasma composed of electrons, positively charged ions andneutral atoms. A plasma generated in the above gases produces highintensity predominantly continuum light radiation with diffuse maxima inthe region of from about 3,000 to about 6,000 Angstroms. The radiationsource can also be used with reflectors or refractive optical systems todirect the high intensity predominantly continuum light radiationemanating from the arc to a particular point or direction or geometricalarea.

The coating compositions of this invention are readily cured by exposureto the radiation for a shorter period of time. The exposure can varyfrom a period as short as a fraction of a second to a period that may beas long as ten minutes or longer. In most instances a period of fromabout 0.1 second to about two minutes is adequate. The distance of thecomposition from the radiation source will vary depending upon theparticular energy source being employed. It can vary from a fraction ofan inch up to 10 feet or more; preferably the distance is from about onefoot to about 4 feet. Exposure can be under normal atmosphericconditions or under an inert gas blanket, for example under nitrogen;the preferred process includes the use of an inert gas atmosphere.

Alternatively, one can add a peroxidic compound, a perester, peracid,peroxide, hydroperoxide, or a persulfate or azo compound to thecomposition and then cure or crosslink by heating at from about 50° C.to about 250° C. The amount of such compound added can vary from about0.1 to about 10 weight percent, preferably 0.5 to about 2.5 weightpercent, of the composition. Any of these compounds known to be usefulin the curing of polymer compositions can be used, such as, di-t-butylperoxide, dicumyl peroxide, t-butyl hydroperoxide, alpha-tetralinhydroperoxide, t-butyl peracetate, peracetic acid, perbenzoic acid,benzoyl peroxide, dichlorobenzoyl peroxide, ammonium persulfate,azobis(isobutyronitrile), dimethyl azobis(isobutyrate), and the like.

ILLUSTRATIVE EXAMPLES PREPARATION OF ACRYLATED EPOXIDIZED SOYBEAN OILCOMPOUNDS Example 1

A mixture was prepared containing 300 parts by weight of a commerciallyavailable epoxidized soybean oil and 47.5 parts by weight of acrylicacid. The epoxidized soybean oil had an average molecular weight ofabout 1,000, an oxirane content of about 7 percent by weight and it wasthe epoxide of the triester of glycerol with soybean oil. The mixturewas heated at 40° C. for 70 hours and then cooled. The reaction productcontained 38.6 parts of unreacted acrylic acid with the balance of thereaction product being acrylated epoxidized soybean oil having anoxirane content of 5.2 percent and an acrylyl content of 0.354milliequivalents per gram.

Example 2

A mixture was prepared using 250 parts of the same epoxidized soybeanoil used in Example 1 and 216 parts of acrylic acid; and it was thenstirred at 125° C. for one hour in an open reaction vessel. Aftercooling to room temperature it was diluted with diethyl ether. Themixture was washed several times with one percent aqueous sodium acidphosphate and then with one percent aqueous sodium chloride solutions.The diethyl ether was removed in vacuo and the product dried. Thereaction product contained 49 parts of unreacted acrylic acid and thebalance, 417 parts, was acrylated epoxidized soybean oil having anoxirane content of 0.2 percent, an acrylyl content of 2.2milliequivalents per gram and a viscosity of 1,500 centistokes at 25° C.by the Gardner method.

Example 3

A mixture was prepared using 100 grams of the same epoxidized soybeanoil used in Example 1, 400 grams of ethylbenzene and 0.2 gram oftridecylphosphite; it was stirred at 90° C. under a nitrogen purge forone hour. Five hundred grams of acrylic acid, 0.006 gram ofphenothiazine, 0.056 gram of hydroquinone and 0.025 gram of alloocimenewere added to the above mixture and stirring was continued for anotherthree hours at 90° C. to 100° C. while purging with oxygen. Theunreacted acrylic acid and the solvent were removed by flashdistillation under vacuum at 120° C. The acrylated epoxidized soybeanoil had an oxirane content of 0.93 percent, an acrylyl content of 2.1milliequivalents per gram and a viscosity of 1,850 centistokes at 100°F. by the Gardner method; the distilled product also contained 0.54percent unreacted acrylic acid.

Example 4

Two liters of the epoxidized soybean oil used in Example 1, 8 liters ofacrylic acid, 8 grams of hydroquinone, 2 grams of p-methoxyphenol and0.5 gram of phenothiazine were charged to a reaction flask and reactedat 100° C. to 110° C. for five hours while continuously purging dry airthrough the mixture. The unreacted acrylic acid was distilled undervacuum on a rotary film evaporator and the residual product was dilutedwith diethyl ether. The solution was passed through a column of aminecontaining ion exchange resin sold commercially as A-21 (Rohm & Haas)and then distilled to remove the diethyl ether. The acrylated epoxidizedsoybean oil was a straw yellow color and was free of unreacted acrylicacid.

PREPARATION OF URETHANE DERIVATIVES OF ACRYLATED EPOXIDIZED SOYBEAN OILCOMPOUNDS Example 5

One hundred parts by weight of acrylated epoxidized soybean oil,produced as described in Example 4, were mixed with 10 parts of methylisocyanate, 30 parts of anhydrous tetrahydrofuran and 0.05 part ofdibutyltin dilaurate in an amber glass bottle and the bottle was sealed.The mixture was agitated at room temperature for twelve hours. Theurethane of the acrylated epoxidized soybean oil contained units of thefollowing formula in the molecule: ##STR5## This structure was confirmedby infrared analysis. The amber-colored urethane had a viscosity of1,000 poises.

Example 6

Two hundred parts by weight of acrylated epoxidized soybean oil,produced as described in Example 4, were dissolved in 100 parts ofdiethyl ether and then 6 parts of an 80/20 mixture of the 2,4- and 2,6-tolylenediisocyanate isomers and 0.05 part of dibutyltin dilaurate wereadded. After agitating in a closed vessel at room temperature for 12hours the diethyl ether was distilled under vacuum. The amber-coloredurethane had a viscosity of 110 poises. The structure of the urethane ofthe acrylated epoxidized soybean oil was confirmed by infrared spectrum;it contained units of the following formula in the molecule: ##STR6##

Example 7

Ninety five parts by weight of acrylated epoxidized soybean oil,produced as described in Example 4, were mixed with 5 parts ofmethylenebis-4,4'-phenyl isocyanate and 0.05 part of dibutyltindilaurate and agitated at 50° C. in a closed reactor for 16 hours. Theyellow urethane of the acrylated epoxidized soybean oil had a Brookfieldviscosity of 3,300 centiposies at 25° C. and contained units of thefollowing formula: ##STR7##

PREPARATION OF AMINE DERIVATIVES OF ACRYLATED EPOXIDIZED SOYBEAN OILCOMPOUNDS Example 8

Ninety seven parts by weight of acrylated epoxidized soybean oil,produced as described in Example 4, were reacted with three parts ofdiethanolamine in a closed vessel for one hour. The aminated acrylatedepoxidized soybean oil was light yellow and it had a Brookfieldviscosity of 17,900 centipoises at 25° C. Analysis indicated that about14 percent of the double bonds of the acrylyl group had reacted with thediethanolamine; the compound contained units of the formula: ##STR8##

Example 9

In a manner similar to that described in Example 8, 97 parts of theacrylated epoxidized soybean oil and 3 parts of morpholine were reactedat 25° C. for one hour. The morpholine adduct of the acrylatedepoxidized soybean oil was amber in color and it had a Brookfieldviscosity of 19,000 centipoises at 25° C. Analysis indicated that about14 percent of the double bonds of the acrylated epoxidized soybean oilhad reacted with the morpholine; the compound contained units of theformula: ##STR9##

PREPARATION OF COATING COMPOSITIONS Example 10

The urethane of acrylated epoxidized soybean oil, produced as describedin Example 6 by the reaction of acrylated soybean oil with two weightpercent of an 80/20 mixture of 2,4- and 2,6- tolylenediisocyanate, wascoated on steel panels. The panels were placed in a flat box coveredwith polyethylene film, purged with nitrogen and irradiated withelectrons from a 300 kilovolt electron accelerator to impart a dose of0.5 megarad to the coating. The coating cured to hard, tough surfaceshaving the following properties.

    ______________________________________                                               Run         A         B                                                ______________________________________                                        Sward hardness (glass = 100)                                                                      8        20                                               Reverse impact (inch-lbs)                                                                        >165      25                                               Acetone resistance (rub cycles)                                                                  16        50                                               Boiling water resistance,                                                     (30 min. immersion)                                                                              good      excellent                                        ______________________________________                                    

Example 11

Coating compositions were produced by the addition of varying amounts of2-hydroxyethyl acrylate (HEA) to the same urethane derivative ofacrylated epoxidized soybean oil used in Example 10. The coatings wereapplied to steel panels and were then irradiated with five megarads ofhigh energy electrons in the same manner described in Example 10; Runs Ato C. In addition, coating compositions were produced from theunmodified acrylated epoxidized soybean oil and 2-hydroxyethyl acrylateand similarly irradiated; Runs D to G. As is evident from the results,the addition of the 2-hydroxyethyl acrylate lowers the viscosity makingthe coating solution easier to apply, while at the same time theproperties of the coatings improved with the increased concentrationthereof used.

    ______________________________________                                                                    Sward     Reverse                                       HEA      Viscosity    hardness  impact                                  Run   wt%      cps at 25° C.                                                                       glass = 100                                                                             in-lbs.                                 ______________________________________                                        A      0       25,000         20        25                                    B     20       1,840          20        100                                   C     30       750            28        165                                   D      0       6,800          12        50                                    E     20       1,200          14        100                                   F     30       390            14        >165                                  G     40       210            14        >165                                  ______________________________________                                    

Example 12

To the acrylated epoxidized soybean oil compound of Example 7 there wasadded 5 weight percent of benzophenone as photosensitizer. Thecomposition was coated on to steel panels and irradiated for sixtyseconds under two side-by-side 550 watt medium pressure mercury arcs.The compositions cured to smooth, hard, clear coatings which resisted200 acetone rub-cycles.

Example 13

A composition was prepared containing 70 parts by weight of theacrylated epoxidized soybean oil compound prepared as described inExample 4 and 30 parts of 2-hydroxyethyl acrylate; it had a viscosity of390 centipoises at 25° C. The composition was coated on steel panelswhich were irradiated as described in Example 10 with varying amounts ofhigh energy electrons to determine the effect of varying the electrondosage on the properties of the cured film. It was found that a dose oftwo megarads was sufficient, a higher dose showed little furtherimprovement. The results are tabulated below; all coatings had a reverseimpact of greater than 165 in-lbs.

    ______________________________________                                                Sward        Acetone    Boiling water                                         hardness     resistance,                                                                              resistance                                    Megarads                                                                              glass = 100  rub-cycles 30 min.                                       ______________________________________                                         0.25   2            11         fair                                          0.5     8            15         good                                          1.0     8            30         good                                          2.0     14           46         good                                          5.0     14           50         good                                          ______________________________________                                    

Example 14

A composition was prepared containing 80 parts of acrylated epoxidizedsoybean oil produced as described in Example 4 and 20 parts of2-butoxyethyl acrylate. This composition was used to produce coatingcompositions containing varying amounts of tricyclo[5.2.1.0².6]dec-3-en-8(-9)-yl acrylate (DCPA), which were coated on steel panelsand cured in the manner described in Example 10. A dosage of 2.5megarads was applied to each panel. The coatings cured to smooth, clearfilms. All of the films had an acetone resistance of 50 rub-cycles andafter 30 minutes immersion in boiling water had a boiling waterresistance rating of excellent. The data is recorded below:

    ______________________________________                                                Sward             Reverse                                             DCPA    hardness          impact,                                             wt.%    glass = 100       in-lbs                                              ______________________________________                                        0       12                5                                                   12.5    16                25                                                  25.0    22                >165                                                37.5    34                >165                                                ______________________________________                                    

Example 15

A composition was produced containing 95 parts by weight of thediethanolamine adduct of Example 8 and 5 parts by weight ofbenzophenone. The solutions were coated on steel panels and irradiatedfor 10 seconds as described in Example 12 to produce a clear, smooth,tack-free coating.

A composition containing 75 parts by weight of the adduct of Example 8,20 parts by weight of neopentyl glycol diacrylate and 5 parts by weightof benzoin butyl ether cures to a clear, hard coating when it isirradiated in a similar manner.

Example 16

A coating composition was produced by mixing 95 parts by weight of themorpholine adduct of Example 9 and 5 parts by weight of benzophenone.The solution was coated on steel panels and irradiated with twoside-by-side 2.2-kilowatt medium-pressure mercury arcs housed indirectional reflectors placed 18 inches over and parallel to a conveyorline moving at 76 feet per minute. A single pass of the coated panelunder the mercury arcs cured the composition to a clear, tack-freecoating.

Example 17

Ninety-five parts by weight of an acrylated epoxidized soybean oilproduced as described in Example 4 and five parts by weight ofbenzophenone were mixed to form a uniform solution. This was coated onsteel panels and irradiated as described in Example 16; three passesunder the mercury arcs were required to cure the composition to atack-free state. A comparison with Example 16 indicates that the amineadducts cure more rapidly.

What is claimed is:
 1. Acrylated epoxidized soybean oil urethanecompounds having in the molecule the group: ##STR10## wherein X ishydrogen or methyl, said compounds being the reaction product of:(A)epoxidized soybean oil reacted with acrylic acid or methyacrylic acidand (B) an organic isocyanate.
 2. A compound as claimed in claim 1wherein (A) is the reaction product of epoxidized soybean oil withmethacrylic acid.
 3. A compound as claimed in claim 1 wherein (A) is thereaction product of epoxidized soybean oil with acrylic acid.
 4. Acompound as claimed in claim 3 wherein (B) is methyl isocyanate.
 5. Acompound as claimed in claim 3 wherein (B) is tolylene diisocyanate. 6.A compound as claimed in claim 3 wherein (B) is methylenebis-4,4'-phenyldiisocyanate.